Production of detonatable explosive emulsion preparations



United Sates Patent The present invention relates to improvements indetonatable explosion emulsion preparations and more.

particularly to a water-in-oil emulsion of water, an emulsifier, and anexplosive component.

Heretofore, water has been added to gelatinous explosives together withglue, dextrin, and starch, the latter three components being used tobind the water added.

Also of interest have been emulsions of liquid nitric acid.

esters and water, but only with a view to solving the delicatetransportation problems attendant explosive materials. A particularpossibility is known for the safe transportation of nitroglycerin, i.e.explosive oil generally of the nitric acid ester type, by conducting thenitroglycerin through a pipe line in the form of an emulsion producedwith water. This conventional technique using a water emulsion withnitroglycerin, as demonstrated by extensive tests, is no longer in sucha condition.

that dangerous detonation may be propagated. Unfortunately, however,these emulsions may only be kept stable under quite specific flowconditions, as for example, those which exist in a flow pipe positionedat an incline.

Therefore, many attempts have been made to improveupon explosivepreparations whereby the same will be safe when transported, yet willprovide the needed detonating properties at the end point of use. Oneattempt in this connection has been to increase the stability ofemulsions of water with nitroglycerin by the incorporation of certainemulsifiers and even through the further.

inclusion of emulsifying auxiliary agents. Nevertheless, independentlyof the type of production procedure, the nitroglycerin-water-emulsionmust possess as a prime condition, the ability to be safely transportedin a manner that the preparation no longer possesses an explosivecharacter, i.e. such preparation must no longer be capable ofpropagating a detonative conversion initiated at a given place. Thevarious known emulsions include both oil-in-water and water-in-oil typeemulsions.

It is an object of the present invention to provide a detonatableexplosive emulsion preparation which is safe to transport in itsprepared condition, yet will be capable of exerting the explosive forcedesired at the point of end use Other and further objects of theinvention will become apparent from a study of the within specificationand accompanying examples.

It has been found in accordance with the present invention that adetonatable explosive emulsion preparation may be provided whichcomprises a water-in-oil emulsion of water, an emulsifier, and anexplosive component, whereby safety in transport will be possible aswell as effective explosive force at the point of controlled detonation.The water-in-oil emulsion may contain up to 72% water whereas theemulsifier may be present in an amount of from about 0.05 to 5% byweight based upon the total emulsion preparation, and preferably in anamount of about 1% by weight.

A stabilizer for the explosive component may be optionally included inthe emulsion preparation, as for example collodion cotton (normally usedfor explosives) with a priming cap #8.

' 0.5 gram zinc-oxy stearate.

or polyvinylacetate, e.g., with about 20 monomers in the chain.

The explosive component of the preparation may be in the form of aliquid or a fused compound, such at nitroglycerin or trinitrotoluene.

The emulsifier used in the preparation in accordance with the inventionmay be an ionic or non-ionic substance. Specifically, the ionicsubstance may be a metal salt of a long-chain fatty acid, and moreparticularly a member selected from the group consisting of alkalineearth-, magnesium-, aluminumand zinc-salts of parafiin fatty acids,oleic acid, parafiin oxy-fatty acids, abietic acid, and mixturesthereof. On the other hand, the nonionic emulsifier may include a memberselected from the group consisting of glycerin-stearates, abietic acidderivatives, polyglycol ethers of ethylene oxide, adducts of higherfatty amines and ethylene oxide, polyvinyl alcohols, esters oflong-chain fatty acids and highef alcohols, and mixtures thereof.

In its broadest aspects, therefore, the present invention contemplatesan aqueous emulsion capable of detonation in which the aqueous phase isemulsified in the form of fine droplets in the explosive component. TheWater-in-oil emulsion is produced actually with the aid of emulsifiersof water and liquid or fused explosive components. Regardless of thefact that the explosive component may be liquid or solid, suitably, theexplosive component must be fusible, eg a fusible oil or a fusiblesolid. The particular emulsion preparation may be carried out in theconventional manner using the emulsifiers as they are added for theproduction of water-in-oil emulsions of the normal type. The specificionic emulsifier substances which may be used include the alkalineearth-, magnesium-, aluminumand zinc-salts of the paraffin fatty acids,oleic acid and the long-chain oxyacids such as the lithium, calcium,magnesium, aluminum and zinc salts of stearic acid, palmetic acid,oxy-stearic acid, oleic acid, and other long-chain carboxylic acids,etc. The non-ionic emulsifier substances may include, as aforesaid,glycerin stearates, abietic acid, and abietic acid derivatives, such asalkyl esters and metal salts, polyglycol-ether of ethylene oxide,adducts of higher fatty amines and ethylene oxide, polyvinyl alcohols,and esters of long-chain fatty acids with higher alcohols, such aslanolin, etc.

It will be appreciated that while the water-in-oil emulsions of theforegoing type may contain up to 72% water, with the emulsifiersubstance concentration ranging between 0.05 and 5%, preferably about1%, based upon the emulsion, it is still possible to vary within a widerange the qauntity of water actually contained in the emulsion.Naturally, the stability of the water-in-oil emulsion is improved by theaddition of a stabilizer, such as, for example collodion-cotton.

The following examples are set forth to establish the differences withrespect .to explosive properties of waterin-oil type emulsions (typeW/O) as opposed to the known oil-in-water emulsion of nitroglycerin(explosive oil)/water (type O/W), .it being understood that theseexamples are by way of illustration and not limitation.

EXAMPLE 1 A water-in-oil emulsion is produced from 50 cc. nitroglycerine(explosive oil) representing a mixture of 60 parts nitroglycerin and 40parts nitroglycol, 55 cc. waiter and As stabilizer, 0.5 gramcollodion-cotton are added. This aqueous emulsion is capable ofdetonation and exhibited in the lead-lock test according to Trauzl in aquantity of 10 grams, a bulging of 225 cubic centimeters, the emulsionbeing detonated It is quite clear from this example that the foregoingwater-in-oil emulsion absolutely possesses the character of anexplosive.

In contrast thereto, an analogously composed emulsion, to which had beenadded, in place of the zinc oxy stearate and collodion-cotton,corresponding quantities of sodium-cetyl sulphate and methyl celluloseas emulsifying agent so as to present an emulsion of the oil-in-waterty-pe, could no longer be detonated with a priming cap #8. Accordingly,this preparation did not exhibit any bulging of the lead-block as wasthe case with the emulsion preparation in accordance with the invention,and therefore the oil-in-water emulsion of the conventional type cannotbe considered an explosive.

EXAMPLE 2...

Using a Water-in-oil emulsion of 75 cc. nitroglycerin explosive oil), 25cc. water, 0.5 gram of partially acetylated polyvinyl alcohol, and 1gram collodion-cotton, a lead block bulging of 410 cubic centimeters wasobtained in accordance with the procedure of Example 1.

EXAMPLE 3 In accordance with the procedure of Example 1, awater-in-oil-emulsion of 50' cc. nitroglycerin (explosive oil), 50 cc.water, 0.5 gram magnesium-oleate, and 0.3 gram collodion-cotton showed alead-block bulging of 220 cubic centimeters.

EXAMPLE 4 Using the procedure of Example 1, a water-in-oil emulsion of75 cc. nitroglycerin (explosive oil), 25 cc. water, 0.5 :gramcalcium-stearate and 2 grams collodioncotton, a lead-block bulging of415 cubic centimeters was obtained.

EXAMPLE 5 In accordance with the procedure of Example 1, using awater-in-oil emulsion of 45 cc. nitroglycerin (explosive oil), 55 cc.water, 0.5 gram zinc stearate, and 2 grams collodion-cotton, alead-block bulging of 215 cubic centimeters was obtained.

EXAMPLE 6 In accordance with the procedure of Example 1, using awater-in-oil emulsion of 40 cc. nitroglycerin (explosive oil), 60 cc.water, 0.5 gram polyglycol monostearyl ether (Peregal O) and 2 gramscollodion-cotton, a lead-block bulging of 110 cubic centimeters wasobtained.

EXAMPLE 7 In acordance with the procedure of Example 1, using awater-in-oil emulsion of 35 cc. nitroglycerin (explosive oil), 65 cc.water, 0.5 gram long-chain fatty acid of a higher alcohol (lanolin) and1 gram collodion-cotton, a lead-block bulging of 75 cu. centimeters wasobtained.

EXAMPLE 8 In accordance with the procedure of Example 1, using awater-in-oil emulsion of 30 cc. nitroglycerin (explosive oil), 70 cc.water, 0.6 gram zinc-12-oxy-stearate and 1 gram collodion-cotton, alead-block bulging of 25 cu. centimeters was obtained.

EXAMPLE 9 At 90 degrees C., various TNTH O-emulsi0ns were produced usingan addition of 0.5% collodion-cotton and 1% calcium stearate. Thetrinitrotoluene (TNT)-water emulsions so prepared were poured intocardboard tubes having an inside diameter of 30 mm. After cooling,stable solid emulsions were obtained which were placed on lead slabs of6 mm. thickness and tested by ignition with pressed tetryl(trinitrophenylmethylnitramine) at a dosage of 25 grams to determine thedetonation capacity of the particular emulsions. The following tableindicates the results obtained:

Table TNT, H2O, Detonation capacity and/or percent percent brisance(Shattering power) 77. 5 21 Lead slab completely ruptured. 63. 5 35 Leadslab barely ruptured. 46. 5 52 Lead slab strongly crushed-in. 30. 5 68Lead slab barely crushed-in.

Accordingly, the great advantage of the emulsions capable of detonation,as produced in accordance with the present invention, is the fact thatthe consistency of the mixtures of ingredients may be varied almost atrandom. By the particular selection of the amounts of the two liquids,to be emulsified, and the quantity of the stabilizer desired,preparations may be obtained which are pourable, creamy, foamy, syrupy,pulpy, gelatinous, pasty, fat-like or wax-like, brittle or massive solidmasses. Because of these characteristics, the emulsion preparationsproduced in accordance with the invention are capable of detonationunder the desired conditions but are safe in transport, rendering themwidely applicable in explosion practice. The emulsion preparations inaccordance with the invent-ion have characteristics of impact(percussion) sensitiveness, and friction sensitiveness which may bevaried within wide limits depending upon the amount of water added tothe emulsion. These properties could not have been expected, sincenitroglycerin is an explosive oil which is present in the emulsion as anundivided phase. Hence, a gelatin preparation of cc. nitroglycerin(explosive oil) (60/40), 1 gram collodioncotton and 0.5 gram zinc-l2-oxystearate may be detonated under a drop hammer according to Kast (PostsChemisch-Techniscke Analyse, 3rd Ed. (1909), vol. II, No. 3) using a 2kg. weight and a dropping height of 60 centimeters. If half the volumequantity of the nitroglycerin (explosive oil) present in the gelatin isreplaced by water so as to form an oil-in-water emulsion, no explosivedetonation is obtained even with a 10 kg. weight and a dropping heightof 60 centimeters.

It will be appreciated from the foregoing that by reason of theparticular water-in-oil emulsion of water, an emulsifier, and anexplosive component, in accordance with the invention, a safelytransportable mass is obtained which is still able to .be detonatedunder reasonable detonat-ing conditions at the point of end use, usingnormal detonation impact values.

What is claimed is:

1. Detonatable explosive emulsion preparation which consists essentiallyof a water-in-oil emulsion of water, an emulsifier, and nitroglycerine,and additionally containing a stabilizer selected from the groupconsisting of collodion cotton and polyvinyl acetate, said water beingpresent in an amount between about 21 and 72% by weight, said emulsifierbeing present in an amount between about 0.05 and 5% by weight and saidstabilizer being present in an amount between about 0.3 and 2 grams per100 cc. of the mixture of the water and nitroglycerine present, and saidemulsifier being selected from the group consisting ofglycerine-stearates, alkyl esters of abietic acid, metal salts ofabietic acid, polyglycol ethers of ethylene oxide, adducts of higherfatty amines and ethylene oxide, polyvinyl alcohols, esters of longchain fatty acids and higher alcohols, mixtures of the foregoing, andmetal salts of long chain fatty acids.

2. Detonatable explosive emulsion preparation which consists essentiallyof a water-in-oil emulsion of water, an emulsifier, and nitroglycol, andadditionally containing a stabilizer selected from the group consistingof collodion cotton and polyvinyl acetate, said water being present inan amount between about 21 and 72% by Weight, said emulsifier beingpresent in an amount between about 0.05 and 5% by weight and saidstabilizer being present in an amount between about 0.3 and 2 grams per100 cc. of the mixture of the water and nitroglycol present, and saidemulsifier being selected from the group consisting ofglycerine-stearates, alkyl esters of abietic acid, metal salts ofabietic acid, polyglycol ethers of ethylene oxide, adducts of higherfatty amines and ethylene oxide, polyvinyl alcohols, esters of longchain fatty acids and higher alcohol-s, mixtures of the foregoing, andmetal salts of long chain fatty acids.

3. Detonatable explosive emulsion preparation which consists essentiallyof a water-in-oil emulsion of water, an emulsifier, and trinitrotoluene,and additionally containing a stabilizer selected from the groupconsisting of collodion cotton and polyvinyl acetate, said water beingpresent in an amount between about 21 and 72% by weight, said emulsifierbeing present in an amount between about 0.05 and 5% by weight and saidstabilizer being present in an amount between about 0.3 and 2 grams per100 cc. of the mixture of the water and triuitrotoluene present, andsaid emulsifier being selected from the group consisting ofglycerine-ste-arates, alkyl esters of abietic acid, metal salts ofabietic acid, polyglycol ethers of ethylene oxide, adducts of higherfatty amines and ethylene oxide, polyvinyl alcohols, esters of longchain fatty acids and higher alcohols, mixtures of the foregoing, andmetal salts of long chain fatty acids.

4. Detonatable explosive emulsion preparation which consists essentiallyof a water-in-oil emulsion of water, an emulsifier, and nitroglycerine,said water being present in an amount between about 21 and 72% by weightand said emulsifier being present in an amount between about 0.05 and 5%by weight, and said emulsifier being selected from the group consistingof glycerine-stearates, alkyl esters of abietic acid, metal salts ofabietic acid, polyglycol ethers of ethylene oxide, adducts of higherfatty amines and ethylene oxide, polyvinyl alcohols, esters of longchain fatty acids and higher alcohols, mixtures of the foregoing, andmetal salts of long chain fatty acids.

5. Detonatable explosive emulsion preparation which consists essentiallyof a water-in-oil emulsion of water, an emulsifier, and nitroglycol,said water being present in an amount between about 21 and 72% by weightand said emulsifier being present in an amount between about 0.05 and 5%by weight, and said emulsifier being selected from the group consistingof glycerine-stearates, alkyl esters of abietic acid, metal salts ofabietic acid, polyglycol ethers of ethylene oxide, adducts of higherfatty amines and ethylene oxide, polyvinyl alcohols, esters of longchain fatty acids and higher alcohols, mixtures of the foregoing, andmetal salts of Ion-g chain fatty acids.

6. Detonatable explosive emulsion preparation which consists essentiallyof a water-in-oil emulsion of Water, an emulsifier and trinitroto luene,said 'water being present in an amount between about 21 and 72% byweight and said emulsifier being present in an amount between about 0.05and 5% by weight, and said emulsifier being selected from the groupconsisting of glycerine-stearates, alkyl esters of abietic acid, metalsalts of abietic acid, polyglycol ethers of ethylene oxide, adducts ofhigher fatty amines and ethylene oxide, polyvinyl alcohols, esters oflong chain fatty acids and higher alcohols, mixtures of the foregoing,and metal salts of long chain fatty acids.

References Cited by the Examiner UNITED STATES PATENTS 1,999,828 4/1935Wiggam 149-101 X CARL D. QUARFORTH, Primary Examiner.

LEON D. ROSDOL, Examiner.

1. DETONATABLE EXPLOSIVE EMULSION PREPARATION WHICH CONSISTS ESSENTIALLYOF A WATER-IN-OIL EMULSION OF WATER, AN EMULSIFIER, AND NITROGLYCERINE,AND ADDITIONALLY CONTAINING A STABILIZER SELECTED FROM THE GROUPCONSISTING OF COLLODON COTTON AND POLYVINYL ACETATE, SAID WATER BEINGPRESENT IN AN AMOUNT BETWEEN ABOUT 21 AND 72% BY WEIGHT, SAID EMULSIFERBEING PRESENT IN AN AMOUNT BETWEEN ABOUT 0.05 AND 5% BY WEIGHT ANDSTABILIZER BEING PRESENT IN AN AMOUNT BETWEEN ABOUT 0.3 AND 2 GRAMS PER100 CC. OF THE MIXTURE OF THE WATER AND NITROGLYCERINE PRESENT, AND SAIDEMULSIFER BEING SELECTED FROM THE GROUP CONSISTING OFGLYCERINE-STEARATES, ALKYL ESTERS OF ABIETIC ACID, METAL SALTS OFABIETIC ACID, POLYGLYCOL ETHERS OF ETHYLENE OXIDE, ADDUCTS OF HIGHERFATTY AMINES AND ETHYLENE OXIDE, POLYVINYL ALCOHOLS, ESTERS OF LONGCHAIN FATTY ACIDS AND HIGHER ALCOHOLS, MIXTURES OF THE FOREGOING, ANDMETAL SALTS OF LONG CHAIN FATTY ACIDS.